Haloalkenyloxyalkyl phosphorothioates



ates and to methods of making same.

United States Patent O 3,028,302 HALOALKENYLOXYALKYL PHOSPHORO- THIGATES John P. Chupp, Kirkwood, Mo., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed May 2, 1960, Ser. No. 25,822 21 Claims. (Cl. 16722) resented by the structure ROX wherein R and R are like or unlike lower alkyl radicals (e.g. methyl, ethyl, propyl, butyl, amyl, and the various isomeric forms thereof containing not more than 5 carbon I atoms); wherein X is a chalkogen of atomic weight less than 40 (i.e. sulfur or oxygen); wherein A is a divalent aliphatic hydrocarbon radical having the empirical formula C H wherein n is a whole number from 1 to 3, inclusive; wherein R is a halogen substituted lower alk- 2-enyl radical (i.e. an allylic structure containing 3 to 5 carbon atoms) wherein the halogen has an atomic number above 9 but not higher than 35 (i.e. chlorine or bromine).

It is preferred that R and R contain not more than two carbon atoms, that A be CH and that R" be wherein B and Y are either hydrogen or methyl or chlorine and wherein Z is hydrogen or chlorine, at least one of B, Y and Z being chlorine. It is particularly preferred that X be sulfur and that R" be a chloroallyl radical of the formula -CH C H,,Cl wherein a is an integer from Oto 2, inclusive.

The phosphorothioates of this invention can be prepared by reacting a salt (i.e. ammonium or alkali metal such as sodium, potassium or lithium) of a phosphorothioic acid of the structure PSH , wherein R, R and X have the aforedescribed significance with a substantially equimolar amount of a halide of the structure Halogen-AOR" wherein A and R have the aforedescribed significance and wherein the term halogen means a halogen having an atomic number above 9 but not higher than 35 (e.g.

chlorine or bromine) in the presence of an inert organic As illustrative of the phosphorothioates of this inven- 0 tion are:

S-(2-bromoallyloxyniethyl) O,()-dimethyl phosphorodi- 'thioate a S-(2-rnethyl-3-chloroallyloxyrnethyl S-(2-chloroallyloxymethyl) 3,028,302 Patented Apr. 3, 1962 ice S-(3-chloroa1lyloxymethy1) 0,0-dimethyl phosphorodithioate S(3,3-dichloroallyloxymethyl) 0,0-dimethyl phosphorodithioate S-(3-chloro-but-2-enyl-oxymethyl) 0,0-dimethyl phosphorodithioate S-[1-(2-chloroallyloxy)ethyl] 0,0-dimethyl phosphorodithioate S-(2-chloroallyloxymethyl) 0,0-diethyl phosphorothioate S-(3,B-dichloroallyloxymethyl) O,O-dietl1yl phosphorothioate 0,0-diethyl phosphorodithioate S(2,3,3-trichloroallyloxymethyl) 0,0-diethyl phosphorodithioate S-(3-chloro-but-2-enyl-oxymethyl) 0,0-diethyl phosphorodithioate S-(2,3-dichloro-but2-enyl-oxymethyl) 0,0-diethyl phosphorodithioate S-(2,3-dichloro-4-bromo-but-2-enyl-oxymethyl) 0,0-diethyl phosphorothioate S-(3,3-dichloroallyloxymethyl) 0,0-diisopropyl phosphorothioate S-(3,3-dichloroallyloxymethyl) 0,0-diisopr0pyl phosphorodithioate S-(Z-bromoallyloxymethyl) 0,0-di-n-butyl phosphorodithioate S-(Z-chloroallyloxymethyl) 0,0-diisoamyl phosphorodithioate S-[2-(3,3-dichloroallyloxy) ethyl] 0,0-diethyl phosphort dithioate S- [2- 3 ,3-dichloroallyloxy propyl] '0,0-diethyl phosphorodithioate S-[3-(2,3,3-trichloroallyloxy)propyl] 0,0-diethyl phosphorodithioate S-(2,3-dichloro-3-bromo-n-pent-2-eny1oxymethyl) 0,0-

dimethyl phosphorodithioate 0,0-diethyl phosphorodithioate' S- i 1- 2-methyl-3 ,3-dichloroallyloxy) ethyl] 0,0-dimethyl phosphorodithioate 'As illustrative of the preparation of the thioates of this invention is the following:

phosphoro- To 32.5 parts by weight 0.16 mole) of ammonium 0,0-diethyl phosphorodi-thioate dissolved in parts by weight of acetone contained in a reaction vessel equipped with a reflux condenser, agitator and thermometer is added 21.2 parts by weight (0.1-5 mole), of chloromethyl 2-chloroallyl ether (i.e. ClCH OCH CC1=CH The mixture is heated for 3 hours at reflux, cooled and filtered. The filter cake is washed with acetone and the combined filtrate and washings stripped of acetone under vacuum. The residue is taken up with 120 parts of methylene chloride, washed with 3% sodium carbonate solution and then with water. The so-washed organic solution is then stripped of methylene chloride to a final pot temperature of C. at 5 mm. pressure to yield 41.5 parts of 0,0-diethyl S-(2-chloroallyloxymethy1) 'phosphorodithioate, an amber liquid which is soluble in benzene but insoluble in Water. Analysis: Theory 22.0% S, 12.2% C1. Found 21.8% S, 12.4% C1.

Example II 0 Cl (CzHrO)r-:l SCH2-O CH2--CH: Employing the same procedure as in Example I but employing ammonium 0,0-diethyl phosphorothioate inplace of ammonium 0,0-.diethyl phosphorodithioate in the same molar amount there is obtained 37.6 parts by weight of 0,0:diethyl S+(2-chloroa1lyloxymethyl) phosphorothioate, an amber oil which is soluble in benzene but insoluble in water. Analysis: Theory 11.2% P, 11.6% S, 12.9% C1. Found 10.7% P, 11.2% S, 13.7% C1.

Example Ill Employing the same procedure as in Example I but employing ammonium O,-O-diethyl phosphorothioate in place of ammonium O,O-diethyl phosphorodithioate in the same molar amount and employing chloromethyl 3,3-dichloroallyl ether (i.e. ClCH OCH CH=CCl in place of chloromethyl 2-chloroallyl ether in the same molar amount there is obtained 28.8 parts of 0,0-diethyl SA( 3,3- dichloroallyloxymethyl) phosphorothioate, an amber oil which is soluble in ethanol but insoluble in water. Analysis: Theory 10.0% P, 10.5%, 23.0% C1. Found 9.6% P, 10.6% s, 22.8% c1.

Example IV Employing the same procedure as in Example. I but,

employing chloromethyl 3,3-dichloroallyl ether in place of chloromethyl 2-chloroallyl ether 'in the same molar amount there is obtained 31.2 parts of 0,0-diethyl S- (3,3-dichloroallyloxymethyl) phosphorodithioate, an amber oil which is soluble in chloroform but insoluble in,

water. Analysis: Theory 9.5% P, 19.7% s, 21.8% c1. Found 9.0% P, 19.9%. S, 21.8% Cl.

Example V II i C1 (01Hion-P-s-em-ofcnl-o;=b-om Employing the same procedure as in Example I but employing chloromethyl 2,3-dichlorobut-2-enyl ether (i.e. ClCH OCH CCl=CClCH in place of chloromethyl 2- chloroallyl ether there is obtained 0,0-dieth yl S-(2,'3- dichlorobut-2-enyloxymethyl) phosphorodithioate, an oil which is soluble in chloroform but insoluble in water.

Example VI u i (CH aO)2 P-S-CHQO:CHZC=CHI Employing the same procedure as in Example I but employing ammonium 0,0-dime'thyl phosphorodithioate in place of ammonium 0,0-diethyl phosphorodithioate in the same molar amount, there is obtained 0,0-dimethyl S-(2-chloroallyloxymethyl) phosphorodithioate, an oil which is soluble in benzene but insoluble inwater.

in place of chloromethyl 2-ch1oroallyl ether in the same molar amount there. is. obtained 0,0-diethy1 S-.(allyloxymethyl) phosphorodithioate (021150)2%sOH2Q-CH1CH=CH2 an amber oil which is soluble in benzene and. chloroform but insoluble in water.

The method by which the phosphorothioates ofthis invention are isolated will vary slightly with the reactants employed and the product-produced. Further purification by selective solvent extraction or by absorptive agents such as activated carbon or clays can precede the removal of the inert organic liquid or solvent. Additionally an inert organic solvent can be added to and in thepurification by absorptive agents. However, the product is generally satisfactory for insecticidal purposes without further purification.

It will be understood that the terms insect and insecticide are used herein in their broad common usage to include spiders, mites, ticks, and like pests which are not in the strict biological sense classed as insects. Thus, the usage herein conforms to the definitions provided by Congress in Public Law 104; the Federal Insecticide, Fungicide, and Rodenticide Act of 1947, section 2, subsection h, wherein the term insect is used to refer not only to those small invertebrate animals belonging mostly to the class Insecta, comprising six-legged, usually winged forms, as beetles, bugs, bees, flies, and so forth, but also to the allied. classes of; arthropods whose members are Wingless and usuallyhavemore than six legs, as spiders, mites, ticks, centipedes, and wood lice.

The phosphorothioates of this invention are efiective against a wide variety of insect pests. As illustrative of the activity but not limitative thereof is the following:

One gram of S-(2-chloroallyloxymethyl) 0,0-diethyl phosphorodithioate is dissolved in sufiicient acetone to make a concentratesolution thereof. Approximately 0.1 cc. of sorbitan monolaurate polyoxyethylene derivative (:1 commercial water-soluble non-ionic emulsifying agent) is then mixed with. the concentrate. To this mixture and with agitation is added sufiicientwater to provide an aqueous emulsion having a concentration of 0.1% .by weight of S-(2-chloroallyloxymethyl) 0,0-diethyl phosphorodithioate. Thereupon lima bean plant leaves previously infested with the two spotted spider mite, T etranychus telarius (L.), are dip'pedjn the aqueous emulsion, withdrawn, and set aside for observation. At the end of 48 hours a 90% kill of the mobile stage of the mite is noted. Seven days after setting the test specimen aside residual activity is confirmed, a 90% kill. of the resting stage and a 90% kill of the ova stage being noted. Similar results against the mobile, resting and ova stages of the same mite are obtained employing S-(Z-chloroallyloxymethyl) 0,0-diethyl phosphorothioate instead of S- (2-chloroallyloxymethyl) 0,0-diethyl phosphorodithioate at a concentration of 0.1%. In contrast in the same test employing S-(allyloxymethyl) 0,0-diethyl phosphorodithioate at the same concentration no kills against either the mobile, resting or ova stagesis observed.

Employing the following:

" S-(2-chloroallyloxymethyl) 0,0-diethyl phosphorodithioate,

S (3,3 dichloroallyloxymethyl) 0,0-diethyl phosphorodithioate,

S (3,3 dichloroallyloxymethyl) 0,0-diethyl phosphorothioate, and

S-(allyloxymethyl) 0,0-diethyl phosphorodithioate,

at respective. concentrations of 0.0001%, 0.0003%., 0.001% and 0.001% by weight; againstyellow fever mosquito larvae Aedes aegypti, respective kills of 90%, and 10% are observed.

Acetone solutions of each of the following:

S-(Z-chloroallyloxymethyl) 0,0-diethyl phosphorodithio-- ate,

S-(3,3-dichloroallyloxymethyl) 0,0-diethyl phosphorodithioate, and S-(3,3 dichloroallyloxymethyl) 0,0-diethy1 phosphorothioate applied as residual treatment to filter paper at a rate of one mg. per square foot gives respective kills of 100% of the adult red flour beetle (Tribolium castaneum).

Although the phosphorothioates of this invention are useful per se in controlling a wide variety of insect pests, it is preferable that they be supplied to the pests or to the environment of the pest or pests in a dispersed form in a suitable extending agent.

In the instant specification and appended claims it is to be understood that the term dispersed is used in its widest possible sense. When it is said that the phosphorothioates of this invention are dispersed, it means that the particles of the phosphorothioates of this invention may be molecular in size and held in true solution in a suitable organic solvent. It means further, that the particles may be colloidal in size and distributed throughout a liquid phase in the form of suspensions or emulsions or in the form of particles held in suspension by wetting agents. It also includes particles which are distributed in a semisolid viscous carrier such as petrolatum or soap or other ointment base in which they may be actually dissolved in the semi-solid or held in suspension in the semi-solid with the aid of suitable wetting or emulsifying agents. The term dispersed also means that the particles may be mixed with and distributed throughout a solid carrier providing a mixture in particulate form, e.g. pellets, granules, powders, or dusts. The term dispsered also includes mixtures which are suitable for use as aerosols including solutions, suspensions, or emulsions of the phosphorothioates of this invention in a carrier such as dichlorodifluoromethane and like fluorochloroalkanes which boil below room temperature at atmospheric pressure.

In the instant specification and appended claims it is to be understood that the expression extending agent includes any and all of those substances in which the phos phorothioates of this invention are dispersed. It includes, therefore, the solvents of a true solution, the liquid phase -of suspensions, emulsions or aerosols, the semi-solid carrier of ointments and the solid phase of particulate solids, e. g. pellets, granules, dusts and powders.

The exact concentration of the phosphorothioates of this invention employed in combatting or controlling insect pests can vary considerably provided the required dosage (i.e., toxic or lethal amount) thereof is supplied to the pests or to the environment of the pests. When the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the phosphorothioate employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a semisolid or solid, the concentration of the phosphorothioate employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. From a practical point of view, the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared insecticidal spray or particulate solid. In such a concentrate composition, the phosphorothioate generally will be present in a concentration of 5 to 95 percent by weight, the residue being any one or more of the well-known insecticidal adjuvants, such as the various surface active agents (e.g. detergents, a soap or other emulsifying or wetting agent, surface-active clays), solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.

There are a large number of organic liquids which can be used for the preparation of solutions, suspensions, or emulsions of the phosphorothioates of this invention.

For example, isopropyl ether, acetone, methyl ethyl ketone, dioxane, cyclohexanone, carbon tetrachloride, ethylene dichloride, tetrachloroethane, hexane, heptane and like higher liquid alkanes, hydrogenated naphthalenes, solvent naphtha, benzene, toluene, xylene, petroleum fractions (e.g. those boiling almost entirely under 400 F'., at atmospheric pressure and having a flash point above about F., particularly kerosene), mineral oils having an unsulfonatable residue above about 80 percent and preferably above about percent. In those instances wherein there may be concern about the phytoxicity of the organic liquid extending agent a portion of same can be replaced by such low molecular weight aliphatic hydrocarbons as dipentene, diisobutylene, propylene trirner, and the like or suitable polar organic liquids, such as the aliphatic ethers and the aliphatic ketones containing not more than about 10 carbon atoms as exemplified by acetone, methyl ethyl ketone, diisobutyl ketone, dioxane, isopropyl ether, and the like. In certain instances, it is advantageous to employ a mixture of organic liquids as the extending agent.

When the phosphorothioates of this invention are to be supplied to the insect pests or to the environment of the pests as aerosols, it is convenient to dissolve them in a suitable solvent and disperse the resulting solution in dichlorodifluoromethane or like chlorofluoroalkane which boils below room temperature at atmospheric pressure.

The phosphorothioates of this invention are preferably supplied to the insert pests or to the environment of the insect pests in the form of emulsions or suspensions. Emulsions or suspensions are prepared by dipersing the phosphorothioate of this invention either per se or in the form of an organic solution thereof in water with the aid of a water-soluble surfactant. The term surfactan as employed here and in the appended claims is used as in volume II of Schwartz, Perry and Berchs SurfaceActive Agents and Detergents (1958, Interscience Publishers, Inc., New York) in place of the expression emulsifying agent to connote generically the various emulsifying agents, dispersing agents, wetting agents and spreading agents that are adapted to be admixed with the active compounds of this invention in order to secure better wetting and spreading of the active ingredients in the water vehicle or carrier in which they are insoluble through lowering the surface tension of the water (see also Frear, Chemistry of Insecticides, Fungicides and Herbicides, second edition, page 280). These surfactants include the well-known capillary-active substances which may be anion-active (or anionic), cation active (or cationic), or nonionizing (or non-ionic) which are described in detail in volumes I and II of Schwartz, Perry and Berchs Surface Active Agents and Detergents (1958, Interscience Publishers, Inc., New York) and also in the November 1947 issue of Chemical Industries (pages 811-824) in an article entitled Synthetic Detergents by John W. McCutcheon and also in the July, August, September and October, 1952 issues of Soap and Sanitary Chemicals under the title Synthetic Detergents. The disclosures of these articles with respect to surfactants, i.e. the anion active, cation active and non-ionizing capillary active substances, are incorporated in this specification by reference in order to avoid unnecessary enlargement of this specification. The preferred surfactants are the water-soluble anionic surfaceactive agents and the water soluble non-ionic surfaceactive agents set forth in US. 2,846,398 (issued August 5, 1958). In general it is preferred that a mixture of watersoluble anionic and water-soluble non-ionic surfactants be employed.

The phosphorothioates of this invention can-be dispersed by suitable methods (e.g., tumbling or grinding) in solid extending agents either of organic or inorganic nature and supplied to the insect pest environment in particulate form. Such solid materials include for example, tricalcium phosphate, calcium carbonate, kaolin, bole, kieselguhr, talc, bentonite, fullers earth, pyrophillite,

diatoniaceous earth, calcinedmagnesia, volcanic ash, sulfur and the like inorganic solid materials, and include, for example, such materials of organic nature as powdered cork, powdered wood, and powdered walnut shells. The preferred solid carriers are the adsorbent clays, e.g. 'bentonite. These mixtures can be used for insecticidal purposes in the dry form, or, by addition of water-soluble surfactants or wetting agents the dry particulate solids can be rendered wettable by water 'so as to obtain stable aqueous dispersions or suspensions suitable for use as sprays.

Forspecial'purposes the phosphorothioates of this invention can be dispersed in a semi-solid extending agent "such as petrolatum or soap (e.g., sodium stearate or oleate or palmitate 'or mixtures thereof) with or without the ofsolubility' promotors and/ or surfactants or dispersing agents. In' all 'ofthe' forms described above the dispersions can be provided'rea'dy for use in combatting insect pests or 'they can be provided in a concentrated form suitable for mixing with or dispersing in other extending agents. illustrative of a particularly useful concentrate is an intimate mixture of phosphorothioates of thisinvention with a water-soluble surfactant which lowers the surface tension of the water in the weight proportions of 0.1 to

15 parts of surfactant withsufiicient of the phosphorothioate of'this invention to make 100 parts by weight. Such a concentrate'is particularly adapted to be made into a spray for combatting various forms of insect pests (particularly mites) by the addition of'water thereto. As illustrative of such a concentrate is an intimate mixture of 95 .parts by-weight of S-(Z-chloroallyloxymethyl) 0,0-diethyl phosphorodithioa'te and parts by weight'of a water-soluble non-ionic surfactant such as the polyoxyethylene derivative of sorbitan monolaurate.

Another useful concentrate adapted to be made into aspray for comb-atting insectpe'sts (particularly mites) is "asolution (preferably as concentrated as possible) of-a phosphorothioate of this invention in an-organic solvent therefor. The said liquid concentrate preferably contains dissolved therein a minor amount (e.-g.().5 to 10 percent by weight of the weight of the new insecticidal agent) of a surfactant (or emulsifying agent), which surfactant is also water-soluble. As illustrative of-such a concentrate is a solution of S-(2,3-dichloroallyloxymethyl) 0,0-diethyl phosphoro'dithioate in benzene which solution contains dissolved therein a Water-soluble .polyoxyethylene glycol non-ionic surfactant and a watersoluble alkaryl sulfonate anionic surfactant.

Of the surfactants aforementioned in preparing the various emulsifiable, wettable or dispersible compositions orconcentrates of this invention, the anionic and nonionic surfacants are preferred. Of the anionic surfactants, the particularly preferred are the well-known water-soluble alkali metal alkylaryl sulfonates as exemplified by sodium decylbenzene sulfonate and sodium dodecylbenzene sulfonate. Of the non-ionic surfactants, the particularly-preferred are the water-soluble polyoxyethylene derivatives of alkylphenols (particularly isooctylphenol) and the water-soluble polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides such as mannitan or sorbitan.

In all of the various dispersions described hereinbefore for insecticidal purposes, the active ingredients can be oneor more of the compounds of this invention. The compounds of this invention can also be advantageously employed in combination with other pesticides, including, for example, nematocides, bactericides, andjherbicid es. In this manner it is possible to obtain which are effective against a wide variety of pests and other forms of noxious life.

In controlling or combat ting insect pestsgthe phos- 'phorothioates of this invention 'either per-se or compositionscomprising same are supplied to the insect pestsor to their environment in-a lethal or toxic amount. V This can-he done by dispersing 'the' new-ins'ecticidal agent or insecticidal composition comprising same in, on or over "an infested environment or in, on or over 'an environment the insect pests frequent, e.g. agricultural ISOil or othengrowth media or other media infested with the insect pestsor-attractable to the pests for habitational or sustenance or propagational purposes, in any conventional 'fashion which permitscontact between the insect .pests and-thephosphorothioates of this invention. Such dispersing can be brought about by applying the phos- ;phorothioates per-seor sprays-or particulate solid compositions containing same to a-surface infested with the insect pests or attractable to the pests, as for example, the surface of agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g. power dusters, boom and hand sprayers, and spray clusters. -Also for sub-surface application such dispersing can be carried out by simply mixing the new insecticidal agent perse or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the insect ,pests frequent, or byemploying a liquid carrier. for the 'neW insecticidal agent to accomplish sub-surfacepenetration and impregnation therein.

While this invention has been described with respect to certain embodiments, it is to be understood that it is not so limited and that variations and modifications thereof obvious to those skilled'in the art can'bemade without departing-from thespirit and scope thereof.

What is claimed is: a 1. Haloalkenyloxyalkyl phosphorothioates of the structure 'wherein'R and R are lower alkyl radicals; wherein X is a ROX wherein R and R are alkyl radicals containing not more than two carbon atoms; wherein X is a chalkogen of atomic weight less than 40; wherein B is selected from the class consisting of hydrogen, methyl and chlorine;

wherein Y is selected from the class-consisting of hydrogen, methyl, and chlorine; wherein Z is selected from the class consisting of hydrogen and chlorine; and wherein at leastone of B, Y and Z is chlorine.

3. Chloroallyloxymethyl phosphorodithioates of the structure ROS wherein R-and R are alkyl radicals containing not more than two carbon atoms; and wherein R is a chloroallyl radical 'of the formula -CH --C2H,,C1 i V wherein a is an integer'from 0 to 2, inclusive.

4. S-(2-chloroallyloxymethyl) 0,0-diethyl phosphorodithioate.

'5. S-(2-chloroallyloxymethyl) 0,0-diethyl phosphorot-hioate.

6. S-(3,3-dichloroallyloxymethyl) 0,0-diethyl phosphorodithioate.

7. S-(3,3-dichloroallyloxymethyl) 0,0-diethyl phosphorothioate.

8. S-(Z-chloroallyloxymethyl) 0,0-dimethyl phosphorodithioate.

9. The method of making the phosphorothioates of claim 1 which comprises reacting a salt selected from the class consisting of ammonium and alkali metal salts of a phosphorothioic acid of the structure R DUI \PSH wherein R, R and X have the same significance as in claim 1 with a substantially equimolar amount of a halide of the structure Halogen-A-O-R wherein A and R" have the same significance as in claim 1 and wherein halogen means a halogen having an atomic number above 9 but not higher than 35, in the presence of an inert organic solvent.

10. The method for protection of plants against insect attack which comprises applying to the plant an insecticidal amount of at least one compound of claim 1.

11. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent.

12. An insecticidal composition comprising a compound of claim 1 dispersed in an extending agent, the composition containing 0.1 to 25 percent by weight of said compound of claim 1, the extending agent being selected from the group consisting of solid and semi-solid extending agents.

13. An insecticidal composition comprising a compound of claim 1 dispersed in a liquid extending agent, the composition containing 0.001 to 50 percent by weight of said compound of claim 1.

14. An insecticidal composition comprising a compound of claim 2 dispersed in an adsorbent clay, the composition containing 0.1 to 25 percent by weight of said compound of claim 2.

15. An insecticidal concentrate comprising a com- 10 pound of claim 2 and an insecticidal adjuvant, said concentrate containing from 5 to percent by weight of the compound of claim 2.

16. An insecticidal concentrate comprising a compound of claim 2 dispersed in an organic solvent therefor and having dissolved therein a minor amount of a surfactant, said concentrate forming an emulsion with water upon agitation therewith.

17. An insecticidal concentrate adapted to be made into a sprayable composition by the addition of water comprising a compound of claim 2 in admixture with a water-soluble surfactant in the weight proportion of 0.1 to 15 parts of surfactant and suflicient of said compound of claim 2 to make parts by weight.

18. The method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 1.

19. The method of controlling insects which comprises contacting the insects with a toxic amount of a compound of claim 2.

20. The method for protection of plants against insect attack which comprises applying to the plant at least one compound of claim 2.

21. Chloroallyloxymethyl phosphorothioates of the structure i -s-onr-o-n" wherein R and R' are alkyl radicals containing not more than two carbon atoms; and wherein R" is a chloroallyl radical of the formula -CH C H Cl wherein a is an integer from 0 to 2 inclusive.

References Cited in the file of this patent UNITED STATES PATENTS 2,596,076 Hook et al May 6, 1952 FOREIGN PATENTS 1,113,363 France Dec. 5, 1955 215,014 Australia July 26, 1956 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 O28 302 April 3, 1962 John P. Chupp It is hereby certified that srror appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Cqlumn 2, line 70,, the formula should appear as shown below lnstead of as in the patent:

column 3 line 22, for "10.5%," read 10.5% S

Signed and sealed this 14th day of August 1962.,

(SEAL) Attest:

YRNEST w. swwsn DAVID LADD Aztesting Officer Commissioner of Patents 

1. HALOALKENYLOXYALKYL PHOSPHOROTHIOATES OF THE STRUCTURE 